US20130184510A1 - Method for reducing coke deposition - Google Patents
Method for reducing coke deposition Download PDFInfo
- Publication number
- US20130184510A1 US20130184510A1 US13/350,108 US201213350108A US2013184510A1 US 20130184510 A1 US20130184510 A1 US 20130184510A1 US 201213350108 A US201213350108 A US 201213350108A US 2013184510 A1 US2013184510 A1 US 2013184510A1
- Authority
- US
- United States
- Prior art keywords
- alcohol
- fuel
- catalyst
- water
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000571 coke Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008021 deposition Effects 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 168
- 239000000446 fuel Substances 0.000 claims abstract description 147
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000000203 mixture Substances 0.000 claims abstract description 87
- 238000002309 gasification Methods 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims description 40
- 238000000354 decomposition reaction Methods 0.000 claims description 40
- 238000005336 cracking Methods 0.000 claims description 36
- 230000001588 bifunctional effect Effects 0.000 claims description 29
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 32
- 150000001298 alcohols Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- -1 ethanol Chemical compound 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
Definitions
- Coke When hydrocarbons, a primary component of fuel, are heated to high temperatures the hydrocarbons can decompose to form coke, a solid carbonaceous material.
- Coke typically consists of approximately 80% to 95% carbon by weight with the balance comprising sulfur, nitrogen, oxygen, hydrogen, and trace amount of inorganic materials (e.g., ash).
- Coke produced during hydrocarbon decomposition can form deposits on the walls of fuel passages, fuel nozzles and heat exchangers. As these coke deposits build up over time, the flow of fuel through the passage or nozzle can become restricted. Additionally, coke deposits can reduce the effectiveness of heat transfer within heat exchangers. If left unchecked, continued coke deposition on wall surfaces can lead to system failure.
- coke can be produced in the cracking reactor and deposit on the cracking catalyst, thereby poisoning the cracking catalyst. Coke deposits reduce the effectiveness of the cracking catalyst. Poisoned cracking catalysts must be subjected to costly and intensive regeneration processes in order to improve their effectiveness.
- U.S. Pat. No. 7,513,260 (“the '260 patent”) describes using water to remove coke deposits from the walls of heat exchangers.
- water present in a fuel stream reacts with a coke deposit to produce hydrogen and carbon monoxide.
- This concept provides a useful method of reducing coke deposition.
- Water is not soluble in the fuel, however, and the method requires the use of a water/steam supply system to incorporate the water into the fuel. This water/steam supply system adds complexity, cost and weight to the overall fuel delivery system.
- a method for reducing coke deposits includes heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture and delivering the fuel-water mixture to a carbon-steam gasification catalyst.
- the fuel-water mixture reacts with the carbon-steam gasification catalyst such that coke deposits are prevented from remaining in a space near the carbon-steam gasification catalyst.
- a method for preventing coke deposits and removing coke deposits on a fuel passage includes substantially coating a surface of the fuel passage with a carbon-steam gasification catalyst, heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture and delivering the fuel-water mixture past the fuel passage surface.
- the fuel-water mixture reacts with the carbon-steam gasification catalyst to prevent formation of coke deposits and remove formed coke deposits on the fuel passage surface.
- a method for preventing coke deposition and removing coke from a catalytic cracking system includes preparing a bifunctional catalyst within the fluid catalytic cracking system, combining an alcohol with a hydrocarbon feedstock that is to be cracked to form an alcohol-hydrocarbon mixture, heating the alcohol-hydrocarbon mixture to decompose the alcohol to form water and produce a hydrocarbon-water mixture, and delivering the hydrocarbon-water mixture to the bifunctional catalyst.
- the bifunctional catalyst includes a cracking catalyst for cracking hydrocarbons and a carbon-steam gasification catalyst. The cracking catalyst reacts with the hydrocarbons in the hydrocarbon-water mixture to break carbon-carbon hydrocarbon bonds. The water in the hydrocarbon-water mixture reacts with the carbon-steam gasification catalyst to prevent formation of coke deposits and remove formed coke deposits from the bifunctional catalyst.
- FIG. 1 is a block diagram of a fuel system in which fuel is used as a heat sink.
- FIG. 2 is a partial cross-sectional view of a fuel passage of the fuel system of FIG. 1 having coke deposits.
- FIG. 3 is a simplified flow diagram of a method for reducing coke deposits from the walls of the fuel system of FIG. 1 .
- FIG. 4 is a graph showing the rate of coke deposition and the rate of alcohol decomposition as a function of temperature.
- FIG. 5 is schematic representation of a reaction between water in a fuel and a coke deposit on a wall coated with a carbon-steam gasification catalyst.
- FIG. 6 is a simplified flow diagram of a method for reducing coke deposits from catalysts of a fluid catalytic cracking system.
- FIG. 7 is a simplified flow diagram of a general method for reducing coke deposits.
- Coke deposits can form on wall surfaces exposed to elevated temperatures and a fuel or catalysts used in fluid catalytic cracking.
- An alcohol such as ethanol
- the alcohol When exposed to the elevated temperatures necessary for the fuel or feedstock to decompose and form coke deposits, the alcohol decomposes, thermally or catalytically, to produce water in situ.
- the water reacts with a steam-gasification catalyst to remove any nearby coke deposits and prevent the formation of coke deposits.
- the method described herein removes the need for a water/steam supply subsystem or a catalyst regeneration system, thereby reducing costs and complexity and, in the case of aircraft, weight.
- FIG. 1 illustrates a block diagram of fuel system 10 in which fuel is used as a heat sink.
- Fuel system 10 can be any system in which fuel is present at elevated operating temperatures.
- fuel system 10 may be used in gas turbine and hypersonic scramjet applications.
- Fuel system 10 generally includes fuel reservoir 12 , heat exchanger 14 , injector 16 , combustor 18 and fuel passages 20 .
- Hydrocarbon fuel is stored in fuel reservoir 12 and is pumped to heat exchanger 14 through fuel passages 20 when needed. Heat is transferred to the fuel flowing through heat exchanger 14 .
- the fuel is used as a heat sink, allowing another fluid (e.g., cooling air) or a hot surface (e.g., combustor wall) to be cooled.
- Combustor 18 burns the fuel to generate power or propulsion, depending on the application.
- FIG. 2 shows a partial cross-sectional view of heat exchanger 14 .
- hydrocarbon fuel is not stable and deposits coke 22 , or carbon-rich deposits, on wall surfaces 24 of heat exchanger 14 through which the hydrocarbon fuel passes.
- coke deposits 22 continue to build on wall surfaces 24 of heat exchanger 14 . If left unchecked, coke deposits 22 can cause damage and lead to failure of fuel system 10 (shown in FIG. 1 ). To prevent failure of fuel system 10 , coke deposits 22 must be removed from high temperature passages of fuel system 10 .
- FIG. 3 illustrates a simplified flow diagram of one embodiment of a method for reducing coke deposits from wall surfaces 24 of fuel system 10 .
- Method 26 describes a method for reducing coke deposits using water that is generated from the fuel in situ to react with coke.
- Method 26 includes coating a wall surface with a carbon-steam gasification catalyst (step 28 ), adding an alcohol to a fuel (step 30 ), heating the fuel to decompose the alcohol to form water (step 32 ) and delivering the formed fuel-water mixture past the wall surface to remove or prevent the formation of coke deposits (step 34 ). While method 26 is described with particular reference to wall surfaces 24 of heat exchanger 14 , coke deposits 22 can also be removed from other high temperature passages of fuel system 10 where coke may deposit, such as fuel passages, fuel nozzles or fuel valves.
- wall surface 24 is substantially coated with a carbon-steam gasification catalyst.
- the carbon-steam gasification catalyst is coated on wall surfaces 24 where coke deposits 22 are likely to form due to exposure to both fuel and elevated temperatures.
- Carbon-steam gasification catalysts allow water and carbon to react to form hydrogen and carbon monoxide.
- suitable carbon-steam gasification catalysts include, but are not limited to, alkali metal salts and alkaline earth metal salts.
- alkali metal salts include Group 1 elements, such as Na 2 CO 3 , K 2 CO 3 and Cs 2 CO 3 .
- alkaline earth metal salts include Group 2 elements, such as MgCO 3 , CaCO 3 , SrCO 3 and BaCO 3 .
- water is provided to the fuel by decomposition of an alcohol.
- an alcohol is added to the fuel.
- the alcohol is generally added to the fuel before it reaches a temperature at which coke deposits 22 can form.
- any alcohol will be miscible with the fuel used in fuel system 10 .
- the alcohol can be introduced into the fuel by virtually any means.
- the alcohol is added directly to fuel within fuel reservoir 12 .
- the alcohol can be premixed with the fuel before it is added to fuel reservoir 12 .
- the alcohol can be delivered to the fuel before reaching heat exchanger 14 by an alcohol delivery system that delivers alcohol to a fuel stream.
- Exemplary alcohols include, but are not limited to, ethanol, propanols, butanols and combinations thereof. Alcohols having longer carbon chains (i.e. more than 4 carbon atoms) can also be used.
- Primary, secondary and tertiary alcohols are all suitable alcohols. Combining the alcohol(s) and the fuel forms an alcohol-fuel mixture.
- step 32 the combined alcohol-fuel mixture is heated to dehydrate or decompose the alcohol present in the alcohol-fuel mixture.
- the alcohol-fuel mixture absorbs heat energy in heat exchanger 14 .
- the fuel is used as a heat sink to cool another fluid, such as cooling air, or a hot surface, such as a combustor wall. Heat energy is transferred from the hot fluid or hot surface to the fuel in heat exchanger 14 .
- Alcohol dehydration is a reaction in which an alcohol decomposes to produce an olefin and water or an ether and water.
- reactions (1) and (2) shown below illustrate potential ethanol decomposition routes while reaction (3) illustrates a potential t-butanol decomposition route.
- reaction (1) ethanol decomposes to form ethylene (CH 2 CH 2 ), an olefin, and water. This reaction is strongly endothermic.
- reaction (2) ethanol decomposes to form diethyl ether (CH 3 CH 2 OCH 2 CH 3 ) and water. This reaction is slightly exothermic.
- reaction (3) t-butanol decomposes to form isobutylene, an olefin, and water. This reaction is strongly endothermic.
- Alcohol can also react to form water in other ways.
- t-butanol can react with ethanol to produce ethyl t-butyl ether (ETBE) and water as illustrated in reaction (4).
- ETBE is commonly used as an oxygenate gasoline additive.
- the ETBE formed in reaction (4) can decompose to form isobutylene and ethanol according to reaction (5). This reaction is strongly endothermic.
- the ethanol formed in reaction (5) can then decompose according to reactions (1) or (2) above, providing additional water.
- Reactions (1), (3) and (5) are strong endothermic reactions, resulting in a cooler water-fuel mixture than the incoming alcohol-fuel mixture. This allows the water-fuel mixture to absorb additional heat energy from the other fluid flowing through heat exchanger 14 (e.g., cooling air) or hot surface (e.g., combustor wall), thereby increasing the heat sink capacity of the fuel and improving the cooling efficiency of heat exchanger 14 .
- heat exchanger 14 e.g., cooling air
- hot surface e.g., combustor wall
- the alcohol-fuel mixture In order for the reactions above to occur, the alcohol-fuel mixture must be heated to an elevated temperature.
- the reactions can occur without the aid of a catalyst (thermally) or with the aid of a catalyst (catalytically).
- Alcohols in the alcohol-fuel mixture will generally decompose to form water once the alcohol-fuel mixture reaches temperatures above about 426° C. (800° F.) in the absence of a catalyst.
- the exact temperature at which thermal decomposition begins can depend on the type of alcohol (i.e. ethanol, 2-propanol, etc.) combined with the fuel.
- the rate of thermal decomposition and the rate of coke deposition are illustrated in FIG. 4 (generally, the rate of catalytic decomposition of alcohol is higher than that of thermal decomposition).
- curve 38 is a graph comparing the rate of coke deposition (curve 36 ) to the rate of alcohol decomposition (curve 38 ) as a function of temperature. Both curves 36 and 38 show an exponential increase in the rates of reaction with increased temperature. As temperatures increase, the rate of water formation and the rate of coke deposition increase exponentially. Curve 38 , which indicates the rate of thermal decomposition of alcohol, is to the left of curve 36 , which indicates the rate of coke deposition. Thus, the rate of alcohol decomposition (and water formation) is generally higher than the rate of coke deposition at a given temperature.
- Exemplary alcohols for forming water using thermal decomposition include 2-propanol, t-butanol, a mixture of ethanol and t-butanol and combinations thereof.
- An alcohol decomposition catalyst can be used to reduce the activation energy of alcohol decomposition and increase selectivity to water formation in step 32 .
- Alcohol decomposition catalysts can benefit virtually any alcohol mixed with the fuel in step 30 .
- the catalyst is highly selective for reactions that decompose the alcohol to an olefin and water (e.g., reactions (1) and (3) above).
- the alcohol decomposition catalyst is introduced to the fuel in optional step 31 .
- the alcohol decomposition catalyst can be introduced to the fuel in step 31 in a number of ways.
- the alcohol decomposition catalyst is added directly to fuel within fuel reservoir 12 .
- the alcohol decomposition catalyst can be premixed with the fuel before it is added to fuel reservoir 12 .
- the alcohol decomposition catalyst can be delivered to the fuel before reaching heat exchanger 14 by a catalyst delivery system that delivers the alcohol decomposition catalyst to a fuel stream.
- the alcohol decomposition catalyst can be introduced to the fuel along with and at the same time as the alcohol.
- the alcohol decomposition catalyst can be coated on wall surfaces 24 of heat exchanger 14 along with the carbon-steam gasification catalyst.
- alcohols in the alcohol-fuel mixture will generally decompose to form water once the alcohol-fuel mixture reaches temperatures above about 370° C. (700° F.).
- the exact temperature at which catalytic decomposition begins can depend on the type of alcohol (i.e. ethanol, 2-propanol, etc.) combined with the fuel, the strength of the alcohol decomposition catalyst and the amount of alcohol decomposition catalyst present.
- the alcohol decomposition catalyst enables catalytic alcohol decomposition at a lower temperature than thermal decomposition.
- Various alcohol decomposition catalysts can be used to decompose the alcohol in step 32 .
- Catalysis of the alcohol decomposition reaction can be homogeneous or heterogeneous.
- the alcohol decomposition catalyst is an acid catalyst.
- Suitable alcohol decomposition catalysts include zeolites, silica-alumina, heteropolyacid catalysts, transitional metal oxides on an alumina support and combinations thereof.
- heteropolyacid catalysts include tungstosilicic acid, tungstophosphoric acid, molybdosilicic acid and molybdophosphoric acid.
- Various amounts of the alcohol decomposition catalysts can be used.
- the amount of alcohol decomposition catalyst added to the system can depend on catalyst strength and the site of the catalyst (in the fuel or coated on wall surfaces 24 ).
- the alcohol decomposition catalyst(s) is/are added directly to the fuel at a concentration ranging from about 0.01% by weight to about 0.1% by weight.
- a fuel-water mixture is formed. While the water is not miscible with the fuel, the pressure under which the fuel is delivered through fuel system 10 keeps the water and fuel together in the form of a mixture. At the temperatures normally experienced by fuel system 10 , particularly at heat exchanger 14 and farther downstream, the water in the fuel-water mixture is in the form of steam.
- the byproducts formed during alcohol decomposition e.g., olefins, ethers, etc.
- the byproducts are generally carried downstream by the fuel to combustor 18 and are suitable for combustion.
- the byproducts are typically short-chain hydrocarbons and combust more readily than the fuel hydrocarbons, thereby presenting no downstream combustion issues. Furthermore, these byproducts may enhance combustion efficiency.
- step 34 the fuel-water mixture formed in step 32 is delivered past wall surface 24 to remove coke deposits 22 and/or prevent their formation.
- Coke deposits 22 are removed from wall surface 24 of heat exchanger 14 through catalytic carbon-steam gasification.
- wall surface 24 By coating wall surface 24 with a carbon-steam gasification catalyst in step 28 , carbon from coke deposits 22 can react with the water in the fuel to form gaseous hydrogen and carbon monoxide as the fuel-water mixture is delivered past wall surface 24 , thereby removing and/or preventing the formation of coke deposits 22 on wall surface 24 .
- Water present in the fuel reacts with the carbon of coke deposits 22 according to the reaction:
- FIG. 5 illustrates a schematic representation of coke deposit 22 on wall surface 24 of heat exchanger 14 and the chemical reaction at wall surface 24 during catalytic carbon-steam gasification.
- carbon-steam gasification catalyst 40 Prior to passing the fuel-water mixture through heat exchanger 14 , carbon-steam gasification catalyst 40 is coated on wall surfaces 24 of heat exchanger 14 . Carbon-steam gasification catalyst 40 acts to catalyze the reaction of coke with the steam present into the fuel-water mixture. Since water formation generally occurs at a lower temperature than coke formation as noted above, water is already present in the fuel when coke begins to form and deposit on wall surface 24 .
- Any coke near carbon-steam gasification catalyst 40 can react with water to produce hydrogen and carbon monoxide before a coke deposit can form on wall surface 24 , thereby preventing formation of coke deposits 22.
- the hydrocarbon fuel, hydrogen and carbon monoxide are combusted downstream as fuel in combustor 18 .
- the amount of alcohol added to the fuel in step 30 can vary depending on the amount of water needed to remove coke deposits and the type of alcohol added to the fuel. Generally speaking, the amount of water present in the fuel is kept to a minimum. Ideally, the fuel contains only enough water to sufficiently remove coke deposits 22 from wall surface 24 ; surplus water does not provide substantial downstream benefits. Depending on the application (i.e. high rate of coke formation, high temperature, etc.), exemplary embodiments of method 26 will require a fuel-water mixture having between about 0.1% water by weight and about 2% water by weight. In particularly exemplary embodiments, the fuel-water mixture has between about 0.5% water by weight and about 2% water by weight.
- Table 1 illustrates the amounts of various alcohols needed to obtain water concentrations of 0.1%, 0.5%, 1% and 2% by weight. Table 1 assumes that all alcohol present in the alcohol-fuel mixture decomposes. At the temperatures described above, virtually all of the alcohol present in the alcohol-fuel mixture will decompose to form water.
- Alcohol that is not decomposed in step 30 can also form radicals and directly attack coke deposits via the following reactions:
- Hydroxyl radicals formed from the undecomposed alcohol can react with coke deposits to form carbon monoxide and hydrogen radicals.
- some alcohols such as ethanol
- ethanol confer additional benefits to fuel system 10 .
- the decomposition of ethanol (and other alcohols) is strongly endothermic, resulting in a cooler water-fuel mixture than the incoming alcohol-fuel mixture.
- the cooler water-fuel mixture can absorb additional heat energy from the cooling fluid in heat exchanger 14 , improving the heat sink capacity of the fuel.
- the addition of ethanol to the fuel also lowers the fuel's initial boiling point. The reduced boiling point may enable a lower cold-start Mach number.
- the addition of ethanol to the fuel also lowers the fuel's freezing point, reducing the potential for problems associated with fuel at or below its cloud point in cold environments.
- method 26 By generating water in situ from an alcohol, method 26 removes the need for a separate water/steam subsystem to provide water to the fuel stream. Eliminating the water/steam subsystem reduces the complexity of fuel system 10 and removes the costs and weight added by a water/steam subsystem.
- Fluid catalytic cracking is used to convert high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils to gasoline, olefinic gases and other products more valuable than crude oil.
- the fluid catalytic cracking process vaporizes and breaks the long-chain molecules of high-boiling hydrocarbon liquids into much shorter molecules by contacting a crude oil feedstock, at high temperature and moderate pressure, with a fluidized powdered cracking catalyst.
- preheated high-boiling petroleum feedstock containing long-chain hydrocarbon molecules is injected into a catalyst riser where the hydrocarbon feedstock is vaporized and cracked into smaller vapor molecules by contacting and mixing with a hot powdered catalyst.
- the hydrocarbon vapors fluidize the powdered catalyst and the mixture of hydrocarbon vapors and catalyst flows upward to enter a reactor.
- the reactor is a vessel in which the cracked product vapors are separated from the spent catalyst using cyclones within the reactor.
- the spent catalyst flows through a steam stripping section to remove any hydrocarbon vapors before the spent catalyst returns to a catalyst regenerator.
- the cracking reactions produce carbonaceous material (coke) that deposits on the catalyst and quickly reduces the catalyst's reactivity.
- the catalyst is regenerated by burning off the deposited coke with air blown through the regenerator.
- the regeneration process requires removing the spent catalyst from the riser and reactor and heating the spent catalyst in a catalyst regenerator. Additionally, some of the spent catalyst sent to the catalyst regenerator cannot be properly regenerated. The process of burning off the deposited coke can adversely affect the catalyst's activity.
- the catalyst can be damaged by the high temperatures. For instance, the high temperatures required for catalyst regeneration can result in blocked pores on the catalyst material, reducing the availability of potential catalysis sites.
- FIG. 6 shows a simplified flow diagram of one embodiment of a method for reducing coke deposits from catalysts of a fluid catalytic cracking system.
- Method 42 can be used to remove coke deposits from the catalysts used in fluid catalytic cracking applications without the need for a separate catalyst regeneration system, providing significant savings in capital and operational costs.
- Method 42 includes preparing a bifunctional catalyst (step 44 ), combining an alcohol with a hydrocarbon feedstock (step 46 ), heating the feedstock and alcohol to decompose the alcohol to form water and produce a hydrocarbon-water mixture (step 48 ) and delivering the formed hydrocarbon-water mixture to the bifunctional catalyst (step 50 ). While method 42 is described with particular reference to fluid catalytic cracking systems, coke deposits can also be removed from other high temperature cracking systems where coke is formed.
- a bifunctional catalyst includes a cracking catalyst and a carbon-steam gasification catalyst.
- the bifunctional catalyst provides for hydrocarbon cracking and the removal and/or prevention of coke deposits on the bifunctional catalyst.
- the cracking catalyst reacts with the hydrocarbon feedstock to break carbon-carbon bonds and crack hydrocarbons.
- the cracking catalyst can be any catalyst normally used in fluid catalytic cracking operations. Cracking catalysts include zeolites, alumina, silica and combinations thereof.
- the carbon-steam gasification catalyst enables water or steam to react with carbon to produce gaseous hydrogen and carbon monoxide according to reaction (6) above. The reaction between water and carbon (coke) prevents or removes coke deposits from the bifunctional catalyst, including the cracking catalyst.
- the cracking catalyst is fluidized by the vaporized hydrocarbon feedstock and the hydrocarbons are cracked in the catalytic riser.
- Method 42 removes the need for a separate catalyst regeneration process.
- the cracking catalyst does not need to be removed and regenerated from the vaporized hydrocarbon feedstock stream.
- the bifunctional catalyst which includes the cracking catalyst, can be positioned within the fluid catalytic cracking system and remain stationary.
- the bifunctional catalyst can be placed within a fixed bed through which the vaporized hydrocarbon feedstock stream is passed.
- the hydrocarbons and the water present in the vaporized hydrocarbon feedstock stream react with the cracking catalyst and the carbon-steam gasification catalyst, respectively.
- the cracking catalyst of the bifunctional catalyst provides for the breaking of hydrocarbon carbon-carbon bonds and cracking.
- the carbon-steam gasification catalyst of the bifunctional catalyst provides for the removal of any coke deposits on the cracking catalyst of the bifunctional catalyst. In this manner, the bifunctional catalyst can theoretically operate indefinitely as long as water is available in the feedstock stream to prevent coke deposits on the cracking catalyst.
- Steps 46 and 48 are similar to steps 30 and 32 , respectively.
- an alcohol is combined with a hydrocarbon feedstock that is to be cracked to form an alcohol-hydrocarbon mixture.
- the alcohols listed above with respect to step 30 are also suitable for use in step 46 .
- the alcohol-hydrocarbon mixture is heated to decompose the alcohol and form water to produce a water-hydrocarbon mixture.
- the alcohol-hydrocarbon mixture is heated to a temperature greater than about 370° C. (700° F.) to decompose the alcohol.
- Most cracking catalysts are highly selective for allow the alcohol to decompose to form an olefin and water as described in reactions (1) and (3) above. No separate alcohol decomposition catalyst is needed.
- Step 50 is similar to step 34 described above.
- the water-hydrocarbon mixture is delivered to the bifunctional catalyst where contents of the water-hydrocarbon mixture react with the catalyst. Instead of just water reacting with the catalyst as in step 34 , however, both the hydrocarbons and water react with the bifunctional catalyst.
- the hydrocarbons are cracked with the aid of the cracking catalyst. Meanwhile, the water prevents the formation of or removes coke deposits from the bifunctional catalyst as described in reaction (6) above.
- the cracked hydrocarbons are delivered to a downstream processing unit, such as a distillation column, where they are separated and collected.
- the water present in the water-hydrocarbon mixture prevents the poisoning of the bifunctional catalyst, which includes the cracking catalyst, due to coke deposition.
- Utilizing a bifunctional catalyst having a carbon-steam gasification catalyst and generating water within the hydrocarbon feedstock stream removes the need for cyclones, the steam stripping section and the catalyst regenerator.
- method 42 eliminates the need for a separate cracking catalyst regeneration step, reducing both capitol and operational costs associated with the catalytic cracking process.
- FIG. 7 illustrates a simplified flow diagram of one embodiment of a general method for reducing coke deposits.
- Method 52 includes heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture in step 54 and delivering the fuel-water mixture to a carbon-steam gasification catalyst in step 56 .
- Step 54 proceeds as described above in step 32 .
- Step 56 proceeds as described above in step 34 .
- the fuel-water mixture reacts with the carbon-steam gasification catalyst such that coke deposits are prevented from remaining in a space near the carbon-steam gasification catalyst.
Abstract
Description
- When hydrocarbons, a primary component of fuel, are heated to high temperatures the hydrocarbons can decompose to form coke, a solid carbonaceous material. Coke typically consists of approximately 80% to 95% carbon by weight with the balance comprising sulfur, nitrogen, oxygen, hydrogen, and trace amount of inorganic materials (e.g., ash). Coke produced during hydrocarbon decomposition can form deposits on the walls of fuel passages, fuel nozzles and heat exchangers. As these coke deposits build up over time, the flow of fuel through the passage or nozzle can become restricted. Additionally, coke deposits can reduce the effectiveness of heat transfer within heat exchangers. If left unchecked, continued coke deposition on wall surfaces can lead to system failure.
- In fluid catalytic cracking applications, coke can be produced in the cracking reactor and deposit on the cracking catalyst, thereby poisoning the cracking catalyst. Coke deposits reduce the effectiveness of the cracking catalyst. Poisoned cracking catalysts must be subjected to costly and intensive regeneration processes in order to improve their effectiveness.
- U.S. Pat. No. 7,513,260 (“the '260 patent”) describes using water to remove coke deposits from the walls of heat exchangers. According to the '260 patent, water present in a fuel stream reacts with a coke deposit to produce hydrogen and carbon monoxide. This concept provides a useful method of reducing coke deposition. Water is not soluble in the fuel, however, and the method requires the use of a water/steam supply system to incorporate the water into the fuel. This water/steam supply system adds complexity, cost and weight to the overall fuel delivery system.
- A method for reducing coke deposits includes heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture and delivering the fuel-water mixture to a carbon-steam gasification catalyst. The fuel-water mixture reacts with the carbon-steam gasification catalyst such that coke deposits are prevented from remaining in a space near the carbon-steam gasification catalyst.
- A method for preventing coke deposits and removing coke deposits on a fuel passage includes substantially coating a surface of the fuel passage with a carbon-steam gasification catalyst, heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture and delivering the fuel-water mixture past the fuel passage surface. The fuel-water mixture reacts with the carbon-steam gasification catalyst to prevent formation of coke deposits and remove formed coke deposits on the fuel passage surface.
- A method for preventing coke deposition and removing coke from a catalytic cracking system includes preparing a bifunctional catalyst within the fluid catalytic cracking system, combining an alcohol with a hydrocarbon feedstock that is to be cracked to form an alcohol-hydrocarbon mixture, heating the alcohol-hydrocarbon mixture to decompose the alcohol to form water and produce a hydrocarbon-water mixture, and delivering the hydrocarbon-water mixture to the bifunctional catalyst. The bifunctional catalyst includes a cracking catalyst for cracking hydrocarbons and a carbon-steam gasification catalyst. The cracking catalyst reacts with the hydrocarbons in the hydrocarbon-water mixture to break carbon-carbon hydrocarbon bonds. The water in the hydrocarbon-water mixture reacts with the carbon-steam gasification catalyst to prevent formation of coke deposits and remove formed coke deposits from the bifunctional catalyst.
-
FIG. 1 is a block diagram of a fuel system in which fuel is used as a heat sink. -
FIG. 2 is a partial cross-sectional view of a fuel passage of the fuel system ofFIG. 1 having coke deposits. -
FIG. 3 is a simplified flow diagram of a method for reducing coke deposits from the walls of the fuel system ofFIG. 1 . -
FIG. 4 is a graph showing the rate of coke deposition and the rate of alcohol decomposition as a function of temperature. -
FIG. 5 is schematic representation of a reaction between water in a fuel and a coke deposit on a wall coated with a carbon-steam gasification catalyst. -
FIG. 6 is a simplified flow diagram of a method for reducing coke deposits from catalysts of a fluid catalytic cracking system. -
FIG. 7 is a simplified flow diagram of a general method for reducing coke deposits. - A method for reducing or removing coke deposits is described herein. Coke deposits can form on wall surfaces exposed to elevated temperatures and a fuel or catalysts used in fluid catalytic cracking. An alcohol, such as ethanol, is added to the fuel or cracking feedstock. When exposed to the elevated temperatures necessary for the fuel or feedstock to decompose and form coke deposits, the alcohol decomposes, thermally or catalytically, to produce water in situ. The water reacts with a steam-gasification catalyst to remove any nearby coke deposits and prevent the formation of coke deposits. The method described herein removes the need for a water/steam supply subsystem or a catalyst regeneration system, thereby reducing costs and complexity and, in the case of aircraft, weight.
-
FIG. 1 illustrates a block diagram offuel system 10 in which fuel is used as a heat sink.Fuel system 10 can be any system in which fuel is present at elevated operating temperatures. For example,fuel system 10 may be used in gas turbine and hypersonic scramjet applications.Fuel system 10 generally includesfuel reservoir 12,heat exchanger 14,injector 16,combustor 18 andfuel passages 20. Hydrocarbon fuel is stored infuel reservoir 12 and is pumped toheat exchanger 14 throughfuel passages 20 when needed. Heat is transferred to the fuel flowing throughheat exchanger 14. The fuel is used as a heat sink, allowing another fluid (e.g., cooling air) or a hot surface (e.g., combustor wall) to be cooled. After the hydrocarbon fuel has been heated, it is passed throughinjector 16 and delivered tocombustor 18. Combustor 18 burns the fuel to generate power or propulsion, depending on the application. -
FIG. 2 shows a partial cross-sectional view ofheat exchanger 14. At high operating temperatures, hydrocarbon fuel is not stable and deposits coke 22, or carbon-rich deposits, onwall surfaces 24 ofheat exchanger 14 through which the hydrocarbon fuel passes. As hydrocarbon fuel flows throughheat exchanger 14,coke deposits 22 continue to build onwall surfaces 24 ofheat exchanger 14. If left unchecked,coke deposits 22 can cause damage and lead to failure of fuel system 10 (shown inFIG. 1 ). To prevent failure offuel system 10,coke deposits 22 must be removed from high temperature passages offuel system 10. -
FIG. 3 illustrates a simplified flow diagram of one embodiment of a method for reducing coke deposits fromwall surfaces 24 offuel system 10.Method 26 describes a method for reducing coke deposits using water that is generated from the fuel in situ to react with coke.Method 26 includes coating a wall surface with a carbon-steam gasification catalyst (step 28), adding an alcohol to a fuel (step 30), heating the fuel to decompose the alcohol to form water (step 32) and delivering the formed fuel-water mixture past the wall surface to remove or prevent the formation of coke deposits (step 34). Whilemethod 26 is described with particular reference towall surfaces 24 ofheat exchanger 14,coke deposits 22 can also be removed from other high temperature passages offuel system 10 where coke may deposit, such as fuel passages, fuel nozzles or fuel valves. - In
step 28,wall surface 24 is substantially coated with a carbon-steam gasification catalyst. The carbon-steam gasification catalyst is coated onwall surfaces 24 wherecoke deposits 22 are likely to form due to exposure to both fuel and elevated temperatures. Carbon-steam gasification catalysts allow water and carbon to react to form hydrogen and carbon monoxide. Examples of suitable carbon-steam gasification catalysts include, but are not limited to, alkali metal salts and alkaline earth metal salts. Examples of alkali metal salts include Group 1 elements, such as Na2CO3, K2CO3 and Cs2CO3. Examples of alkaline earth metal salts include Group 2 elements, such as MgCO3, CaCO3, SrCO3 and BaCO3. As described in greater detail below, water is provided to the fuel by decomposition of an alcohol. - In
step 30 ofmethod 26, an alcohol is added to the fuel. The alcohol is generally added to the fuel before it reaches a temperature at whichcoke deposits 22 can form. Generally speaking, any alcohol will be miscible with the fuel used infuel system 10. Thus, the alcohol can be introduced into the fuel by virtually any means. In exemplary embodiments, the alcohol is added directly to fuel withinfuel reservoir 12. Alternatively, the alcohol can be premixed with the fuel before it is added tofuel reservoir 12. In other embodiments, the alcohol can be delivered to the fuel before reachingheat exchanger 14 by an alcohol delivery system that delivers alcohol to a fuel stream. Exemplary alcohols include, but are not limited to, ethanol, propanols, butanols and combinations thereof. Alcohols having longer carbon chains (i.e. more than 4 carbon atoms) can also be used. Primary, secondary and tertiary alcohols are all suitable alcohols. Combining the alcohol(s) and the fuel forms an alcohol-fuel mixture. - In
step 32, the combined alcohol-fuel mixture is heated to dehydrate or decompose the alcohol present in the alcohol-fuel mixture. The alcohol-fuel mixture absorbs heat energy inheat exchanger 14. As noted above, the fuel is used as a heat sink to cool another fluid, such as cooling air, or a hot surface, such as a combustor wall. Heat energy is transferred from the hot fluid or hot surface to the fuel inheat exchanger 14. - Alcohol dehydration (or decomposition) is a reaction in which an alcohol decomposes to produce an olefin and water or an ether and water. For example, reactions (1) and (2) shown below illustrate potential ethanol decomposition routes while reaction (3) illustrates a potential t-butanol decomposition route.
-
CH3CH2OH→CH2CH2+H2O (1) -
2CH3CH2OH→CH3CH2OCH2CH3+H2O (2) -
(CH3)3COH→(CH3)2C═CH2+H2O (3) - In reaction (1), ethanol decomposes to form ethylene (CH2CH2), an olefin, and water. This reaction is strongly endothermic. In reaction (2), ethanol decomposes to form diethyl ether (CH3CH2OCH2CH3) and water. This reaction is slightly exothermic. In reaction (3), t-butanol decomposes to form isobutylene, an olefin, and water. This reaction is strongly endothermic.
- Alcohol can also react to form water in other ways. For example, t-butanol can react with ethanol to produce ethyl t-butyl ether (ETBE) and water as illustrated in reaction (4). ETBE is commonly used as an oxygenate gasoline additive.
-
(CH3)3COH+CH3CH2OH→(CH3)3COCH2CH3+H2O (4) - The ETBE formed in reaction (4) can decompose to form isobutylene and ethanol according to reaction (5). This reaction is strongly endothermic. The ethanol formed in reaction (5) can then decompose according to reactions (1) or (2) above, providing additional water.
-
(CH3)3COCH2CH3→(CH3)2C═CH2+CH3CH2OH (5) - Reactions (1), (3) and (5) are strong endothermic reactions, resulting in a cooler water-fuel mixture than the incoming alcohol-fuel mixture. This allows the water-fuel mixture to absorb additional heat energy from the other fluid flowing through heat exchanger 14 (e.g., cooling air) or hot surface (e.g., combustor wall), thereby increasing the heat sink capacity of the fuel and improving the cooling efficiency of
heat exchanger 14. - In order for the reactions above to occur, the alcohol-fuel mixture must be heated to an elevated temperature. The reactions can occur without the aid of a catalyst (thermally) or with the aid of a catalyst (catalytically). Alcohols in the alcohol-fuel mixture will generally decompose to form water once the alcohol-fuel mixture reaches temperatures above about 426° C. (800° F.) in the absence of a catalyst. The exact temperature at which thermal decomposition begins can depend on the type of alcohol (i.e. ethanol, 2-propanol, etc.) combined with the fuel. The rate of thermal decomposition and the rate of coke deposition are illustrated in
FIG. 4 (generally, the rate of catalytic decomposition of alcohol is higher than that of thermal decomposition).FIG. 4 is a graph comparing the rate of coke deposition (curve 36) to the rate of alcohol decomposition (curve 38) as a function of temperature. Both curves 36 and 38 show an exponential increase in the rates of reaction with increased temperature. As temperatures increase, the rate of water formation and the rate of coke deposition increase exponentially.Curve 38, which indicates the rate of thermal decomposition of alcohol, is to the left ofcurve 36, which indicates the rate of coke deposition. Thus, the rate of alcohol decomposition (and water formation) is generally higher than the rate of coke deposition at a given temperature. Exemplary alcohols for forming water using thermal decomposition include 2-propanol, t-butanol, a mixture of ethanol and t-butanol and combinations thereof. - An alcohol decomposition catalyst can be used to reduce the activation energy of alcohol decomposition and increase selectivity to water formation in
step 32. Alcohol decomposition catalysts can benefit virtually any alcohol mixed with the fuel instep 30. In embodiments ofmethod 26 employing an alcohol decomposition catalyst, the catalyst is highly selective for reactions that decompose the alcohol to an olefin and water (e.g., reactions (1) and (3) above). - The alcohol decomposition catalyst is introduced to the fuel in optional step 31. The alcohol decomposition catalyst can be introduced to the fuel in step 31 in a number of ways. In exemplary embodiments, the alcohol decomposition catalyst is added directly to fuel within
fuel reservoir 12. Alternatively, the alcohol decomposition catalyst can be premixed with the fuel before it is added tofuel reservoir 12. In other embodiments, the alcohol decomposition catalyst can be delivered to the fuel before reachingheat exchanger 14 by a catalyst delivery system that delivers the alcohol decomposition catalyst to a fuel stream. In embodiments where an alcohol delivery system is used instep 30, the alcohol decomposition catalyst can be introduced to the fuel along with and at the same time as the alcohol. In still other embodiments, the alcohol decomposition catalyst can be coated on wall surfaces 24 ofheat exchanger 14 along with the carbon-steam gasification catalyst. - In embodiments where an alcohol decomposition catalyst is used, alcohols in the alcohol-fuel mixture will generally decompose to form water once the alcohol-fuel mixture reaches temperatures above about 370° C. (700° F.). The exact temperature at which catalytic decomposition begins can depend on the type of alcohol (i.e. ethanol, 2-propanol, etc.) combined with the fuel, the strength of the alcohol decomposition catalyst and the amount of alcohol decomposition catalyst present. The alcohol decomposition catalyst enables catalytic alcohol decomposition at a lower temperature than thermal decomposition.
- Various alcohol decomposition catalysts can be used to decompose the alcohol in
step 32. Catalysis of the alcohol decomposition reaction can be homogeneous or heterogeneous. In exemplary embodiments, the alcohol decomposition catalyst is an acid catalyst. Suitable alcohol decomposition catalysts include zeolites, silica-alumina, heteropolyacid catalysts, transitional metal oxides on an alumina support and combinations thereof. Examples of heteropolyacid catalysts include tungstosilicic acid, tungstophosphoric acid, molybdosilicic acid and molybdophosphoric acid. Various amounts of the alcohol decomposition catalysts can be used. The amount of alcohol decomposition catalyst added to the system can depend on catalyst strength and the site of the catalyst (in the fuel or coated on wall surfaces 24). In exemplary embodiments, the alcohol decomposition catalyst(s) is/are added directly to the fuel at a concentration ranging from about 0.01% by weight to about 0.1% by weight. - Once the alcohol decomposes in
step 32, a fuel-water mixture is formed. While the water is not miscible with the fuel, the pressure under which the fuel is delivered throughfuel system 10 keeps the water and fuel together in the form of a mixture. At the temperatures normally experienced byfuel system 10, particularly atheat exchanger 14 and farther downstream, the water in the fuel-water mixture is in the form of steam. The byproducts formed during alcohol decomposition (e.g., olefins, ethers, etc.) are generally carried downstream by the fuel to combustor 18 and are suitable for combustion. The byproducts are typically short-chain hydrocarbons and combust more readily than the fuel hydrocarbons, thereby presenting no downstream combustion issues. Furthermore, these byproducts may enhance combustion efficiency. - In
step 34, the fuel-water mixture formed instep 32 is deliveredpast wall surface 24 to removecoke deposits 22 and/or prevent their formation.Coke deposits 22 are removed fromwall surface 24 ofheat exchanger 14 through catalytic carbon-steam gasification. By coatingwall surface 24 with a carbon-steam gasification catalyst instep 28, carbon fromcoke deposits 22 can react with the water in the fuel to form gaseous hydrogen and carbon monoxide as the fuel-water mixture is deliveredpast wall surface 24, thereby removing and/or preventing the formation ofcoke deposits 22 onwall surface 24. Water present in the fuel reacts with the carbon ofcoke deposits 22 according to the reaction: -
C(coke)+H2O→H2+CO (6) -
FIG. 5 illustrates a schematic representation ofcoke deposit 22 onwall surface 24 ofheat exchanger 14 and the chemical reaction atwall surface 24 during catalytic carbon-steam gasification. Prior to passing the fuel-water mixture throughheat exchanger 14, carbon-steam gasification catalyst 40 is coated on wall surfaces 24 ofheat exchanger 14. Carbon-steam gasification catalyst 40 acts to catalyze the reaction of coke with the steam present into the fuel-water mixture. Since water formation generally occurs at a lower temperature than coke formation as noted above, water is already present in the fuel when coke begins to form and deposit onwall surface 24. Any coke near carbon-steam gasification catalyst 40 can react with water to produce hydrogen and carbon monoxide before a coke deposit can form onwall surface 24, thereby preventing formation ofcoke deposits 22. The hydrocarbon fuel, hydrogen and carbon monoxide are combusted downstream as fuel incombustor 18. - The amount of alcohol added to the fuel in
step 30 can vary depending on the amount of water needed to remove coke deposits and the type of alcohol added to the fuel. Generally speaking, the amount of water present in the fuel is kept to a minimum. Ideally, the fuel contains only enough water to sufficiently removecoke deposits 22 fromwall surface 24; surplus water does not provide substantial downstream benefits. Depending on the application (i.e. high rate of coke formation, high temperature, etc.), exemplary embodiments ofmethod 26 will require a fuel-water mixture having between about 0.1% water by weight and about 2% water by weight. In particularly exemplary embodiments, the fuel-water mixture has between about 0.5% water by weight and about 2% water by weight. Since an alcohol has a greater molecular weight than water, the amount of alcohol added to the fuel instep 30 is greater than the desired water concentration. Table 1 below illustrates the amounts of various alcohols needed to obtain water concentrations of 0.1%, 0.5%, 1% and 2% by weight. Table 1 assumes that all alcohol present in the alcohol-fuel mixture decomposes. At the temperatures described above, virtually all of the alcohol present in the alcohol-fuel mixture will decompose to form water. -
TABLE 1 Alcohol (% by weight) needed to reach the listed H2O weight % 0.1% H2O 0.5% H2O by 1% H2O by 2% H2O by by weight weight weight weight Ethanol 0.26 1.28 2.60 5.10 1-Propanol 0.33 1.67 3.34 6.68 2-Propanol 0.33 1.67 3.34 6.68 t-Butanol 0.41 4.12 2.06 8.24 - Alcohol that is not decomposed in
step 30 can also form radicals and directly attack coke deposits via the following reactions: -
R—OH→R.+HO. (7) -
HO.+C(coke)→CO+H. (8) - Hydroxyl radicals formed from the undecomposed alcohol can react with coke deposits to form carbon monoxide and hydrogen radicals.
- In addition to providing a source of water used to remove coke deposits, some alcohols, such as ethanol, confer additional benefits to
fuel system 10. For example, as described above, the decomposition of ethanol (and other alcohols) is strongly endothermic, resulting in a cooler water-fuel mixture than the incoming alcohol-fuel mixture. The cooler water-fuel mixture can absorb additional heat energy from the cooling fluid inheat exchanger 14, improving the heat sink capacity of the fuel. The addition of ethanol to the fuel also lowers the fuel's initial boiling point. The reduced boiling point may enable a lower cold-start Mach number. The addition of ethanol to the fuel also lowers the fuel's freezing point, reducing the potential for problems associated with fuel at or below its cloud point in cold environments. - By generating water in situ from an alcohol,
method 26 removes the need for a separate water/steam subsystem to provide water to the fuel stream. Eliminating the water/steam subsystem reduces the complexity offuel system 10 and removes the costs and weight added by a water/steam subsystem. - The concepts described above can also be applied to fluid catalytic cracking processes used in petroleum refining and other petroleum industry applications. Fluid catalytic cracking is used to convert high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils to gasoline, olefinic gases and other products more valuable than crude oil. In general, the fluid catalytic cracking process vaporizes and breaks the long-chain molecules of high-boiling hydrocarbon liquids into much shorter molecules by contacting a crude oil feedstock, at high temperature and moderate pressure, with a fluidized powdered cracking catalyst.
- In one embodiment of a normal fluid catalytic cracking process, preheated high-boiling petroleum feedstock containing long-chain hydrocarbon molecules is injected into a catalyst riser where the hydrocarbon feedstock is vaporized and cracked into smaller vapor molecules by contacting and mixing with a hot powdered catalyst. The hydrocarbon vapors fluidize the powdered catalyst and the mixture of hydrocarbon vapors and catalyst flows upward to enter a reactor. The reactor is a vessel in which the cracked product vapors are separated from the spent catalyst using cyclones within the reactor. The spent catalyst flows through a steam stripping section to remove any hydrocarbon vapors before the spent catalyst returns to a catalyst regenerator. The cracking reactions produce carbonaceous material (coke) that deposits on the catalyst and quickly reduces the catalyst's reactivity. The catalyst is regenerated by burning off the deposited coke with air blown through the regenerator.
- Because the coke deposits poison the cracking catalysts, a separate catalyst regeneration process is required. The regeneration process requires removing the spent catalyst from the riser and reactor and heating the spent catalyst in a catalyst regenerator. Additionally, some of the spent catalyst sent to the catalyst regenerator cannot be properly regenerated. The process of burning off the deposited coke can adversely affect the catalyst's activity. The catalyst can be damaged by the high temperatures. For instance, the high temperatures required for catalyst regeneration can result in blocked pores on the catalyst material, reducing the availability of potential catalysis sites.
-
FIG. 6 shows a simplified flow diagram of one embodiment of a method for reducing coke deposits from catalysts of a fluid catalytic cracking system.Method 42 can be used to remove coke deposits from the catalysts used in fluid catalytic cracking applications without the need for a separate catalyst regeneration system, providing significant savings in capital and operational costs.Method 42 includes preparing a bifunctional catalyst (step 44), combining an alcohol with a hydrocarbon feedstock (step 46), heating the feedstock and alcohol to decompose the alcohol to form water and produce a hydrocarbon-water mixture (step 48) and delivering the formed hydrocarbon-water mixture to the bifunctional catalyst (step 50). Whilemethod 42 is described with particular reference to fluid catalytic cracking systems, coke deposits can also be removed from other high temperature cracking systems where coke is formed. - In
step 44, a bifunctional catalyst is prepared. A bifunctional catalyst includes a cracking catalyst and a carbon-steam gasification catalyst. The bifunctional catalyst provides for hydrocarbon cracking and the removal and/or prevention of coke deposits on the bifunctional catalyst. The cracking catalyst reacts with the hydrocarbon feedstock to break carbon-carbon bonds and crack hydrocarbons. The cracking catalyst can be any catalyst normally used in fluid catalytic cracking operations. Cracking catalysts include zeolites, alumina, silica and combinations thereof. As described above, the carbon-steam gasification catalyst enables water or steam to react with carbon to produce gaseous hydrogen and carbon monoxide according to reaction (6) above. The reaction between water and carbon (coke) prevents or removes coke deposits from the bifunctional catalyst, including the cracking catalyst. - In the fluid catalytic cracking example described above, the cracking catalyst is fluidized by the vaporized hydrocarbon feedstock and the hydrocarbons are cracked in the catalytic riser.
Method 42 removes the need for a separate catalyst regeneration process. Thus, the cracking catalyst does not need to be removed and regenerated from the vaporized hydrocarbon feedstock stream. Instead, the bifunctional catalyst, which includes the cracking catalyst, can be positioned within the fluid catalytic cracking system and remain stationary. For example, the bifunctional catalyst can be placed within a fixed bed through which the vaporized hydrocarbon feedstock stream is passed. As described in greater detail below, the hydrocarbons and the water present in the vaporized hydrocarbon feedstock stream react with the cracking catalyst and the carbon-steam gasification catalyst, respectively. The cracking catalyst of the bifunctional catalyst provides for the breaking of hydrocarbon carbon-carbon bonds and cracking. The carbon-steam gasification catalyst of the bifunctional catalyst provides for the removal of any coke deposits on the cracking catalyst of the bifunctional catalyst. In this manner, the bifunctional catalyst can theoretically operate indefinitely as long as water is available in the feedstock stream to prevent coke deposits on the cracking catalyst. -
Steps steps step 46, an alcohol is combined with a hydrocarbon feedstock that is to be cracked to form an alcohol-hydrocarbon mixture. The alcohols listed above with respect to step 30 are also suitable for use instep 46. Instep 48, the alcohol-hydrocarbon mixture is heated to decompose the alcohol and form water to produce a water-hydrocarbon mixture. The alcohol-hydrocarbon mixture is heated to a temperature greater than about 370° C. (700° F.) to decompose the alcohol. Most cracking catalysts are highly selective for allow the alcohol to decompose to form an olefin and water as described in reactions (1) and (3) above. No separate alcohol decomposition catalyst is needed. -
Step 50 is similar to step 34 described above. Instep 50, the water-hydrocarbon mixture is delivered to the bifunctional catalyst where contents of the water-hydrocarbon mixture react with the catalyst. Instead of just water reacting with the catalyst as instep 34, however, both the hydrocarbons and water react with the bifunctional catalyst. At the bifunctional catalyst, the hydrocarbons are cracked with the aid of the cracking catalyst. Meanwhile, the water prevents the formation of or removes coke deposits from the bifunctional catalyst as described in reaction (6) above. After the hydrocarbons are cracked instep 50, the cracked hydrocarbons are delivered to a downstream processing unit, such as a distillation column, where they are separated and collected. - The water present in the water-hydrocarbon mixture prevents the poisoning of the bifunctional catalyst, which includes the cracking catalyst, due to coke deposition. Utilizing a bifunctional catalyst having a carbon-steam gasification catalyst and generating water within the hydrocarbon feedstock stream removes the need for cyclones, the steam stripping section and the catalyst regenerator. Thus,
method 42 eliminates the need for a separate cracking catalyst regeneration step, reducing both capitol and operational costs associated with the catalytic cracking process. -
FIG. 7 illustrates a simplified flow diagram of one embodiment of a general method for reducing coke deposits.Method 52 includes heating an alcohol-fuel mixture to decompose alcohol and form water to produce a fuel-water mixture instep 54 and delivering the fuel-water mixture to a carbon-steam gasification catalyst instep 56.Step 54 proceeds as described above instep 32.Step 56 proceeds as described above instep 34. The fuel-water mixture reacts with the carbon-steam gasification catalyst such that coke deposits are prevented from remaining in a space near the carbon-steam gasification catalyst. - While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (20)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/350,108 US9187700B2 (en) | 2012-01-13 | 2012-01-13 | Method for reducing coke deposition |
EP13151184.2A EP2639287B1 (en) | 2012-01-13 | 2013-01-14 | Method for reducing coke deposition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/350,108 US9187700B2 (en) | 2012-01-13 | 2012-01-13 | Method for reducing coke deposition |
Publications (2)
Publication Number | Publication Date |
---|---|
US20130184510A1 true US20130184510A1 (en) | 2013-07-18 |
US9187700B2 US9187700B2 (en) | 2015-11-17 |
Family
ID=47559297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/350,108 Active 2034-09-19 US9187700B2 (en) | 2012-01-13 | 2012-01-13 | Method for reducing coke deposition |
Country Status (2)
Country | Link |
---|---|
US (1) | US9187700B2 (en) |
EP (1) | EP2639287B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104711550A (en) * | 2013-12-13 | 2015-06-17 | 通用电气公司 | Surface treatment method and device treated by surface treatment method |
CN108424785A (en) * | 2018-04-17 | 2018-08-21 | 中国石油大学(华东) | Inferior heavy oil double-reaction tube alkalinity millisecond catalytic pyrolysis and gasification coupling technique |
CN108587674A (en) * | 2018-04-17 | 2018-09-28 | 中国石油大学(华东) | Heavy oil double-reaction tube semicoke circulation fluidized bed millisecond pyrolysis-gasification coupling technique |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105950207B (en) * | 2016-07-07 | 2017-07-18 | 天津大学 | A kind of method for suppressing hydrocarbon fuel cracking furnace pipe tube wall coking |
US20180313225A1 (en) | 2017-04-26 | 2018-11-01 | General Electric Company | Methods of cleaning a component within a turbine engine |
US11707819B2 (en) | 2018-10-15 | 2023-07-25 | General Electric Company | Selectively flexible extension tool |
US11702955B2 (en) | 2019-01-14 | 2023-07-18 | General Electric Company | Component repair system and method |
US11692650B2 (en) | 2020-01-23 | 2023-07-04 | General Electric Company | Selectively flexible extension tool |
US11752622B2 (en) | 2020-01-23 | 2023-09-12 | General Electric Company | Extension tool having a plurality of links |
US11613003B2 (en) | 2020-01-24 | 2023-03-28 | General Electric Company | Line assembly for an extension tool having a plurality of links |
US11371437B2 (en) | 2020-03-10 | 2022-06-28 | Oliver Crispin Robotics Limited | Insertion tool |
US11654547B2 (en) | 2021-03-31 | 2023-05-23 | General Electric Company | Extension tool |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5358626A (en) * | 1993-08-06 | 1994-10-25 | Tetra International, Inc. | Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon procssing |
US20030070963A1 (en) * | 1995-02-17 | 2003-04-17 | Linde Aktiengesellschaft | Process and apparatus for cracking hydrocarbons |
US20040188323A1 (en) * | 2003-03-24 | 2004-09-30 | Tzatzov Konstantin K. | Active coating system for reducing or eliminating coke build-up during petrochemical processes |
US20040256290A1 (en) * | 2002-01-31 | 2004-12-23 | Hidenori Yamada | Catalyst for fluid catalytic cracking of heavy hydrocarbon oil and method of fluid catalytic cracking |
US20080156692A1 (en) * | 2006-12-29 | 2008-07-03 | Petroleo Brasileiro S.A. - Petrobras | Process for converting ethanol and hydrocarbons in a fluidized catalytic cracking unit |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1949588A (en) | 1930-07-18 | 1934-03-06 | Thomas & Hochwalt Lab Inc | Composition for removing carbon deposits |
US2264964A (en) | 1940-07-29 | 1941-12-02 | Pure Oil Co | Composition for treating motors and for addition to motor fuel |
US3849291A (en) | 1971-10-05 | 1974-11-19 | Mobil Oil Corp | High temperature catalytic cracking with low coke producing crystalline zeolite catalysts |
US4418224A (en) | 1981-09-18 | 1983-11-29 | General Electric Company | Preparation of ortho-alkylated phenols using magnesium compound catalysts |
US4590307A (en) | 1983-12-20 | 1986-05-20 | General Electric Company | Catalyst precursor prepared from manganese carbonate, and use of a calcined derivative in an ortho-alkylation process |
US5567305A (en) | 1993-08-06 | 1996-10-22 | Jo; Hong K. | Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing |
DE69809735D1 (en) | 1997-06-05 | 2003-01-09 | Atf Resources Inc | METHOD AND DEVICE FOR REMOVING AND INHIBITING COKSANALGE IN PYROLYSIS |
CN1368540A (en) | 2001-02-01 | 2002-09-11 | 呼世滨 | Anti-explosion additive of gasoline and gasoline prepared from it |
US7334407B2 (en) | 2004-03-22 | 2008-02-26 | United Technologies Corporation | Method of suppressing coke in endothermic fuel processing |
ES2328516T3 (en) | 2005-07-06 | 2009-11-13 | Bp Chemicals Limited | REACTIVE DISTILLATION FOR THE DEHYDRATION OF MIXED ALCOHOLS. |
US7513260B2 (en) | 2006-05-10 | 2009-04-07 | United Technologies Corporation | In-situ continuous coke deposit removal by catalytic steam gasification |
CA2607478A1 (en) | 2007-09-27 | 2009-03-27 | 11 Good's Energy Ltd. | Fuel composition |
WO2009081204A1 (en) | 2007-12-20 | 2009-07-02 | The University Of Bristol | Alcohol dehydration |
US20110107657A1 (en) | 2009-11-10 | 2011-05-12 | Yiyu Chen | Fuel Additive |
KR101545383B1 (en) | 2010-06-23 | 2015-08-18 | 토탈 리서치 앤드 테크놀로지 펠루이 | Dehydration of alcohols on poisoned acidic catalysts |
CN102041112A (en) | 2010-12-27 | 2011-05-04 | 山东福康全环保科技有限公司 | High energy environment-friendly clean gasoline additive |
-
2012
- 2012-01-13 US US13/350,108 patent/US9187700B2/en active Active
-
2013
- 2013-01-14 EP EP13151184.2A patent/EP2639287B1/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5358626A (en) * | 1993-08-06 | 1994-10-25 | Tetra International, Inc. | Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon procssing |
US20030070963A1 (en) * | 1995-02-17 | 2003-04-17 | Linde Aktiengesellschaft | Process and apparatus for cracking hydrocarbons |
US20040256290A1 (en) * | 2002-01-31 | 2004-12-23 | Hidenori Yamada | Catalyst for fluid catalytic cracking of heavy hydrocarbon oil and method of fluid catalytic cracking |
US20040188323A1 (en) * | 2003-03-24 | 2004-09-30 | Tzatzov Konstantin K. | Active coating system for reducing or eliminating coke build-up during petrochemical processes |
US20080156692A1 (en) * | 2006-12-29 | 2008-07-03 | Petroleo Brasileiro S.A. - Petrobras | Process for converting ethanol and hydrocarbons in a fluidized catalytic cracking unit |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104711550A (en) * | 2013-12-13 | 2015-06-17 | 通用电气公司 | Surface treatment method and device treated by surface treatment method |
WO2015088679A1 (en) * | 2013-12-13 | 2015-06-18 | General Electric Company | Surface treatment method and device treated thereby |
JP2017503071A (en) * | 2013-12-13 | 2017-01-26 | ゼネラル・エレクトリック・カンパニイ | Surface treatment method and apparatus treated thereby |
US10138434B2 (en) | 2013-12-13 | 2018-11-27 | General Electric Company | Surface treatment method and device treated thereby |
CN108424785A (en) * | 2018-04-17 | 2018-08-21 | 中国石油大学(华东) | Inferior heavy oil double-reaction tube alkalinity millisecond catalytic pyrolysis and gasification coupling technique |
CN108587674A (en) * | 2018-04-17 | 2018-09-28 | 中国石油大学(华东) | Heavy oil double-reaction tube semicoke circulation fluidized bed millisecond pyrolysis-gasification coupling technique |
Also Published As
Publication number | Publication date |
---|---|
US9187700B2 (en) | 2015-11-17 |
EP2639287B1 (en) | 2024-03-20 |
EP2639287A1 (en) | 2013-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9187700B2 (en) | Method for reducing coke deposition | |
JP2590009B2 (en) | Flow method for converting hydrocarbon-containing raw materials into low molecular weight liquid products | |
JP2020517793A (en) | Improving Light Olefin Yield by Steam Catalytic Downer Pyrolysis of Hydrocarbon Feedstocks | |
CA2878917C (en) | Methods and fuel processing apparatuses for upgrading a pyrolysis oil stream and a hydrocarbon stream | |
US20160090539A1 (en) | Fcc units, apparatuses and methods for processing pyrolysis oil and hydrocarbon streams | |
EP2814913A1 (en) | A process for catalytic conversion of low value hydrocarbon streams to light olefins | |
US8293670B2 (en) | Process for the production of propylene | |
US5324419A (en) | FCC to minimize butadiene yields | |
KR930011920B1 (en) | Process for catalystic cracking of hydrocarbons | |
CN109370644A (en) | A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons | |
JP2007153924A (en) | Biomass treatment method using fluidized catalytic cracking | |
EP3165588B1 (en) | Process for production of syngas through regeneration of coked cracking agent | |
WO2018116085A1 (en) | Process integration for cracking light paraffinic hydrocarbons | |
EP2532727B1 (en) | Process for fluid catalytic cracking | |
US10487279B2 (en) | Production of high yield of syngas through regeneration of coked upgrading agent | |
CN101205477B (en) | Low energy consumption catalytic conversion method of hydrocarbon oil | |
Mccarthy et al. | FCC technology upgrades: A commercial example | |
CA3223811A1 (en) | Heat integration of process comprising a fluid catalyst cracking reactor and regenerator | |
JPS594475B2 (en) | Catalytic cracking method and equipment for heavy oil | |
Ship et al. | Influence of Dimethyl disulfide (DMDS) on the cracking process, a solution to coke formation | |
CN106147823A (en) | A kind of technique of heavy oil contact cracking |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNITED TECHNOLOGIES CORPORATION, CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HUANG, HE;HAAS, MARTIN;REEL/FRAME:027532/0263 Effective date: 20120113 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
AS | Assignment |
Owner name: RAYTHEON TECHNOLOGIES CORPORATION, MASSACHUSETTS Free format text: CHANGE OF NAME;ASSIGNOR:UNITED TECHNOLOGIES CORPORATION;REEL/FRAME:054062/0001 Effective date: 20200403 |
|
AS | Assignment |
Owner name: RAYTHEON TECHNOLOGIES CORPORATION, CONNECTICUT Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE AND REMOVE PATENT APPLICATION NUMBER 11886281 AND ADD PATENT APPLICATION NUMBER 14846874. TO CORRECT THE RECEIVING PARTY ADDRESS PREVIOUSLY RECORDED AT REEL: 054062 FRAME: 0001. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF ADDRESS;ASSIGNOR:UNITED TECHNOLOGIES CORPORATION;REEL/FRAME:055659/0001 Effective date: 20200403 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |
|
AS | Assignment |
Owner name: RTX CORPORATION, CONNECTICUT Free format text: CHANGE OF NAME;ASSIGNOR:RAYTHEON TECHNOLOGIES CORPORATION;REEL/FRAME:064714/0001 Effective date: 20230714 |